TECHNICAL FIELD
[0001] The present invention relates to granular detergent compositions containing a detergent
surfactant, an aluminosilicate ion exchange material, a water-soluble neutral or alkaline
salt and a film-forming polymer. The compositions herein, which contain no cr only
low levels of phosphate materials and less than about 3% by weight of alkali metal
silicate materials, provide granules having both superior free-flowing characteristics
and solubility in the laundering solution.
[0002] Granular detergent compositions have, in tne past, often contained high concentrations
of phosphate builder materials, particularly sodium tripolyphesphate. When a crutcher
mix containing sodium tripolyphosphate is spray-dried, it is believed that enough
mixed-phosphate hydrolysis products are formed to inhibit phosphate crystal growth.
The hydrolysis products are concentrated in the liquid phase which finally dries to
an amorphous glassy phosphate material. This glassy material effectively "cements"
the finely crystalline granule walls together, producing granules which exhibit very
desiraole physical properties, i.e., crisp, durable and free-flowing granules. Moreover,
the glassy phosphate material readily disintegrates in the laundering solution so
that no insoluble residue is left on the fabrics.
[0003] Alkali metal silicates are usually included in granular detergents at low levels
for corrosion inhibition and processing reasons. When phosphate builders are removed
from detergents, the level of silicate is often increased severalfold since it also
dries to a tough glassy film capable of strengthening granule walls and enhancing
free-flowing characteristics. Silicates having a lower SiO
2 to alkali metal oxide ratio (e.g., 1.6-2.0) are usually selected because they are
more water-soluble than the higher ratio silicates. However, exposure of the silicate
to carbon dioxide during drying and storage can shift its ratio to a higher value
and reduce its solubility, resulting in detergent granules which do not completely
disintegrate in the laundering solution, and an unacceptably high level of insoluble
material being deposited on fabrics. The insolubles problem can be particularly severe
when the detergent composition also contains the water-insoluble aluminosilicate material
herein since higher levels of silicates (e.g., above about 3%) enhance the deposition
of the aluminosilicates onto fabrics.
BACKGROUND ART
[0004] U.S. Patent 3,985,669, Krummel, et al., issued October 12, 1976, describes the use
of low levels (i.e., about 0.5% to 3%) of alkali metal silicates in granular detergent
compositions also containing aluminosilicate builder materials to provide both corrosion
inhibition and crispness benefits without enhancing deposition of the aluminosilicates
onto fabrics.
[0005] U.S. Patent 4,072,621, Rose, issued February 7, 1978, discloses the addition of a
water-soluble copolymer of a vinyl compound and maleic anhydride to granular detergents
containing aluminosilicate builders. The compositions provide improved granule physical
properties, particularly relating to reduced dustiness, and improved cleaning performance
in the presence of appreciable amounts of orthophosphate and pyrophosphate, such as
formed by the hydrolysis of polyphosphates during spray-drying operations. The compositions
disclosed in the examples contain 20% by weight of phosphate materials.
[0006] British Patent 2,048,841, published December 17, 1980, discloses the use of polymeric
acrylamides to stabilize aqueous suspensions of zeolites. The suspensions are said
to be suitable for spray-drying to obtain detergent compositions.
[0007] German Patent 2,615,698, published October 20, 1977, describes stable suspensions
containing aluminosilicates, dispersing agents which can include polymers containing
carboxylic and/or hydroxyl groups, and stabilization agents. The suspensions are said
to be useful in the manufacture of spray-dried detergents.
[0008] German-patent 2,854,484, published June 26, 1980, discloses stable zeolite suspensions
containing polyacrylamides or copolymers thereof with acrylic acid. The suspensions
are said to be useful as sequestering agents in spray-dried detergent compositions.
SUMMARY OF THE INVENTION
[0009] The present invention encompasses granular detergent compositions comprising:
(a) from about 5% to about 40% by weight of an organic surfactant selected from the
group consisting of anionic, nonionic, zwitterionic, ampholytic and cationic surfactants,
and mixtures thereof;
(b) from about 10% to about 60% of a finely divided aluminosilicate ion exchange material
selected from the group consisting of:
(1) crystalline aluminosilicate material of the formula:

wherein z and y are at least 6, the molar ratio of z to y is from 1.0 to 0.5 and x
is from 10 to 264, said material having a particle size diameter of from about 0.1
micron to about 10 microns, a calcium ion exchange capacity of at least about 200
mg. CaCO3 eq./g. and a calcium ion exchange rate of at least about 2 grains Ca++/gallon/minute/gram/gallon;
(2) amorphous hydrated aluminosilicate material of the empirical formula:

wherein M is sodium, potassium, ammonium, or substituted anmonium, z is from about
0.5 to about 2 and y is 1, said material having a magnesium ion exchange capacity
of at least about 50 milligram equivalents of CaCO3 hardness per gram of anhydrous aluminosilicate and a Mg exchange rate of at least
about 1 grain/gallon//minute/gram/gallon; and
(3) mixtures whereof;
(c) from about 5% to about 75% by weight of a water-soluble neutral or alkaline salt;
and
(d) from about 0.1% to about 10% by weight of a film-forming polymer soluble in an
aqueous slurry comprising tne above components; said composition containing less than
about 10% by weight of phosphate materials and less than about 3% by weight of alkali
metal silicate materials.
[0010] The film-flowing polymer is preferably represented by a copolymer of acrylamide and
acrylate having a molecular weight of from about 3000 to about 100.000 and an acrylamide
content of less than about 50%.
[0011] The composition further preferably contains from about 0.5% to about 2% of a sodium
or potassium silicate having a molar ratio of SiO
2 to alkali metal oxide of from about 1 to about 1.4.
DETAILED DESCRIPTION OF THE INVENTION
[0012] The granular detergent compositions of the present invention contain, as essential
components, a detergent surfactant, an aluminosilicate ion exchange material, a water-soluble
neutral or alkaline salt and a film-forming polymer, as described hereinafter. The
compositions contain less than about 3%, preferably less than about 2%, by weight
of alkali metal silicate materials and less than about 10%, preferably less than about
5%, by weight of phosphate materials. Most preferably, the compositions are substantially
free of phosphate materials.
[0013] The compositions herein are prepared by drying an aqueous slurry comprising the above
components. The slurry generally contains from about 25% to about 50% water, whereas
the dried granules contain from about 3% to about 15% water. The drying operation
can be accomplished by any convenient means, for example, by using spray-drying towers,
both counter-current and co-current, fluid beds, flash-drying equipment, or industrial
microwave or oven drying equipment. While not intending to be limited by theory, it
is believed that the granular detergents herein exhibit superior free-flowing characteristics
because the film-forming polymer dries to a tough, non-sticky, non-hygroscopic film
which cements the granule walls together much in the same manner as do the glassy
phosphates and silicates. Since the polymer film is readily water-soluble, the granules
quickly disintegrate in the laundering solution and leave little or no insoluble residue
on the fabrics. Moreover, the film-forming polymer does not enhance the deposition
of the aluminosilicate material onto fabrics, as do higher levels of the alkali metal
silicates.
Organic Surfactant
[0014] The detergent compositions herein contain from about 5% to about 40% by weight of
an organic surfactant selected from the group consisting of anionic, nonionic, zwittericnic,
ampholytic and cationic surfactants, and mixtures thereof. The surfactant preferably
represents from about 10% to about 30%, and more preferaoly from about 14% to about
20%, by weight of the detergent composition. Surfactants useful herein are listed
in U.S. Patent 3,664,961, Norris, issued May 23, 1972, and in U.S. Patent 3,919,678,
Lau
ghlin, et al., issued December 30, 1975, ooth incorporated herein by reference. Useful
cationic surfactants also include those described in U.S. Patent 4,222,905, Cockrell,
issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16,
1980, both incorporated herein by reference. However, cationic surfactants are generally
less compatible with the aluminosilicate materials herein, and thus are preferably
used at low levels, if at all, in the present compositions. The following are representative
examples of surfactants useful in the present compositions.
[0015] Water-soluble salts of the higher fatty acids, i.e., "soaps", are useful anionic
surfactants in the compositions herein. This includes alkali metal soaps such as the
sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing
from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon
atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization
of free fatty acids. Particularly useful are the sodium and potassium salts of the
mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium
tallow and coconut soap.
[0016] Useful anionic surfactants also include the water-soluble salts, preferably the alkali
metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having
in their molecular structure an alkyl group containing from about 10 to about 20 carbon
atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl"
is the alkyl portion of acyl groups.) Examples of this group of synthetic surfactants
are the sodium and potassium alk-yl sulfates, especially those obtained by sulfating
the higher alcohols (C
8-C
18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut
oil; and the sodium and potassium alkyl benzene sulfonates in which the alkyl group
contains from about 9 to about 15 carbon atoms, in straight chain or branched chain
configuration, e.g., those of the type describe in United States Patents 2,220,099
and 2,477,383. Especially valuable are linear straight chain alkyl benzene sulfonates
in which the average number of carbon atoms in the alkyl group is from about 11 to
13, abbreviated as C
11-13LAS.
[0017] Other anicnic surfactants herein are the sodium alkyl glyceryl ether sulfonates,
especially those ethers of higher alcohols derived from tallow and coconut oil; sodium
coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium
salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about
10 units of ethylene oxide per molecule and wherein the alkyl groups contain from
about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl etnylene
oxide ether sulfates containing about 1 to about 10 units of ethylene oxide per molecule
and wherein the alkyl group contains from about 10 to about 20 carbon atoms.
[0018] Other useful anionic surfactants herein include the water-soluble salts of esters
of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the
fatty acid group and from about 1 to 10 carbon atoms in the ester grcup; water-soluble
salts of 2-acyloxy-alkane-l-sulfonic acids containing from about 2 to 9 carbon atoms
in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety;
alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group
and from about 1 to 30 moles of ethylene oxide; water-soluble salts of olefin sulfonates
containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing
from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms
in the alkane moiety.
[0019] Water-soluble nonionic surfactants are also useful in the compositions of the invention.
Such nonionic materials include compounds produced by the condensation of alkylene
oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may
be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group
which is condensed with any particular hydrophobic group can be readily adjusted to
yield a water-soluble compound having the desired degree of balance between hydrophilic
and hydrophobic elements.
[0020] Suitable non ionic surfactants include the polyethylene oxide condensates of alkyl
phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing
from about 6 to 15 carbon atoms, in either a straight chain or branched chain configuration,
with from about 3 to 12 moles of ethylene oxide per mole of alkyl phenol.
[0021] Preferred nonicnics are the water-soluble condensation products of aliphatic alcohols
containing from 8 to 22 carbon atoms, in eitner straight chain or branched configuration,
with from 3 to 12 moles of ethylene oxide per mole of alcohol. Particularly preferred
are the condensation products of alcohols having an alkyl group containing from about
9 to 15 carbon atoms with from about 4 to 8 moles of ethylene oxide per mole of alcohol.
[0022] Semi-polar nonionic surfactants include water-soluble amine oxides containing one
alkyl moiety of from about 10 to 18 carbon atoms and 2 moieties selected from the
group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about
3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about
10 to 18 carom atoms and 2 moieties selected from the group consisting of alkyl groups
and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble
sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety
selected from the group consisting of alkyl and hydroxyalkyl moieties of from about
1 to 3 carbon atoms.
[0023] Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives
of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be
straight chain or branched and wherein one of the aliphatic substituents contains
from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an
anionic water-solubilizing group.
[0024] Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium,
and sulfonium compounds in which one of the aliphatic substituents contains from about
8 to 18 carbon atoms.
[0025] Particularly preferred surfactants herein include linear alkylbenzene sulfcnates
containing from about 11 to 14 carbon atoms in the alkyl group; tallowalkyl sulfates;
coconutalkyl glyceryl ether sulfonates; alkyl ether sulfates wherein the alkyl moiety
contains frcm about 14 to 18 carbon atoms and wherein the average degree of ethoxylation
is from about 1 to 4; olefin or paraffin sulfonates co taining from about 14 to 16
carbon atoms; alkyldimethyl amine oxides wherein the alkyl group contains from about
11 to 16 carbon atoms; alkyldimethyiammonio propane sulfonates and alkyldimethylammonio
hydroxy propane sulfcnates wherein the alkyl group contains from about 14 to 18 carbon
atoms; soaps of higher fatty acids containing from about 12 to 18 carbon atoms; condensation
products of C
9-C
15 alcohols with from about 4 to 8 moles of ethylene oxide, and mixtures thereof.
[0026] Specific preferred surfactants for use herein include: sodium linear C
11-13 alkylbenzene sulfonate; triethanolamine C
11-13 alkylbenzene sulfonate; sodium tallow alkyl sulfate; sodium coconut alkyl glyceryl
ether sulfonate; the sodium salt of a sulfated condensation product of a tallow alcohol
with about 4 moles of ethylene oxide; the condensation product of a coconut fatty
alcohol with about 6 moles of ethylene oxide; the condensation product of tallow fatty
alcohol with about 11 moles of ethylene oxide; 3-(N,N-dimethyl-N-coconutalkylammonio)-
2-hydroxypropane-l-sulfonate; 3-(N,N-dimethyl-N-coconutalkylammonio- propane-1-sulfonate;
6-(N-dodecylbenzyl-N,N-dimethylammonio) hexanoate; dodecyi dimethyl amine oxide; coccnut
alkyldimethyl amine oxide; and the water-soluble sodium and potassium salts of coconut
and tallow fatty acids.
Aluminosilicate Ion Exchange Material
[0027] The detergent compositions herein also contain from about 10% to about 60%, preferably
from about 15% to about 40%, and more preferably from about 18% to about 30%, by weight
of crystalline aluminosilicate ion exchange material of the formula

wherein z and y are at least about 6, the molar ration of z to y is from about 1.0
to about 0.5 and x is from about 10 to about 264. Amorphous hydrated aluminosilicate
materials useful herein have the empirical formula

wherein M is sodium, potassium, ammonium or substituted amnonium, z is from about
0.5 to about 2 and y is 1, said material having a magnesium ion exchange capacity
of at least about 50 milligram equivalents of CaCO
3 hardness per gram of anhydrous aluminosilicate.
[0028] The aluminosilicate ion exchange builder materials herein are in hydrated form and
contain from about 10% to about 28% of water by weight if crystalline, and potentially
even higher amounts of water if amorphous. Highly preferred crystalline aluminosilicate
icn exchange materials contain from about 18% to about 22% water in their crystal
matrix. The crystalline aluminosilicate ion exchange materials are further characterized
by a particle size diameter of from about 0.1 micron to about 10 microns. Amorphous
materials are often smaller, e.g., down to less than about 0.01 micron. Preferred
ion exchange materials have a particle size diameter of from about 0.2 micron to about
4 microns. The term "particle size diameter" herein represents the average particle
size diameter of a given ion exchange material as determined by conventional analytical
techniques such as, for example, microscopic determination utilizing a scanning electron
microscope. The crystalline aluminosilicate ion exchange materials herein are usually
further characterized by their calcium ion exchange capacity, which is at least about
200 mg. equivalent of CaCD
3 water hardness/g. of aluminosilicate, calculated on an anhydrous basis, and which
generally is in the range of from about 300 mg. eq./g. to about 352 mg. eq./g. The
aluminosilicate ion exchange materials herein are still further characterized by their
calcium ion exchange rate which is at least about 2 grains Ca
++/gallon/minute/gram/gallon of aluminosilicate (anhydrous basis), and generally lies
within the range of from about 2 grains/gallon/minute/gram/gallon to about 6 grains/gallon/minute/
gram/gallon, based on calcium ion hardness. Optimum aluminosilicate for builder purposes
exhibit a calcium ion exchange rate of at least . about 4 grains/gallon/minute/gram/gallon.
[0029] The amorphous aluminosilicate ion exchange materials usually have a Mg exchange capacity
of at least about 50 mg. eg. CaCO
3/g. (
12 mg.
Mg /g.) and a Mg exchange rate of at least about 1 grain/gallon/minute/gram/gallon.
Amorphous materials do not exhibit an observable diffraction pattern when examined
by Cu radiation (1.54 Angstrom Units).
[0030] Alumincsilicate ion exchange materials useful in the practice of this invention are
commercially available. The aluminosilicates useful in this invention can be crystalline
or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically
derived. A method for producing aluminosilicate ion exchange materials is discussed
in U.S. Patent 3,985,669, Krummel, et al., issued October 12, 1976, incorporated herein
by reference. Preferred synthetic cyrstalline aluminosilicate ion exchange materials
useful herein are available under the designations Zeolite A, Zeolite B, and Zeolite
X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange
material has the formula

wherein x is from about 20 to about 30, especially about 27.
Water-Soluble Neutral or Alkaline Salt
[0031] The granular detergents of the present invention additionally contain from about
5% to about 75%, preferably from about 10% to about 60%, and more preferably from
about 20% to about 50%, by weight of a water-soluble neutral or alkaline salt. The
neutral or alkaline salt has a pH in solution of seven or greater, and can be either
organic or inorganic in nature. The salt assists in providing the desired density
and bulk to the detergent granules herein. While some of the salts are inert, many
of them also function as detergency builder materials in the laundering solution.
[0032] Examples of neutral water-soluble salts include the alkali metal, ammonium or substituted
ammonium chlorides, fluorides and sulfates. The alkali metal, and especially sodium,
salts of the above are preferred. Sodium sulfate is typically used in detergent granules
and is a particularly preferred salt herein.
[0033] Other useful water-soluble salts include the compounds commonly known as detergent
builder materials. Builders are generally selected from the various water-soluble,
alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates,
. polyphospnonates, carbonates, silicates, borates, polyhydroxy- sulfonates, polyacetates,
carboxylates, and polycarboxylates. Preferred are the alkali metal, especially sodium,
salts of the above. Howerve, as previously described, the present compositions contain
less than about 3%, preferably less than about 2%, by weight of silicate materials
and less than about 10%, preferably less than about 5%, by weight cf phosphate materials.
Most preferably, the compositions are substantially free of phosphates.
[0034] Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphate,
pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about
6 to 21, and orthophosphate. Examples of polyphosphonate builders are the sodium and
potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane
1-hyarexy-1,1-dipnosphonic acid and the sodium and potassium salts of ethane, 1,1,2-triphosphonic
acid. Other phosphorus builder compounds are disclosed in U.S. Patents 3,159,581;
3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, incorporated herein by reference.
[0035] Examples of non-phosphorus, inorganic builders are sodium and potassium carbonate,
bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a molar
ratio of SiO
2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to
about 2.4.
[0036] Water-soluble, non-phosphorus organic builders useful herein include the various
alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates
and polyhydroxy- sulfonates. Examples of polyacetate and polycarboxylate builders
are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene
diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid,
benzene polycarboxylic acids, and citric acid.
[0037] Highly preferred polycarboxylate builders herein are set forth in U.S. Patent No.
3,308,067, Diehl, issued March 7, 1967 incorporated herein by reference. Such materials
include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids
such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic
acid and methylenemalonic acid.
[0038] Other useful builders herein are sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate,
cis-cyclo- hexanehexacarboxylate, cis-cyclopentanetetracarboxylate phloroglucinol
trisulfonate, and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.
[0039] Other suitable polycarboxylates for use herein are the polyacetal carboxylates described
in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfiled, et al., and U.S. Patent
4,246,495, issued March 27, 1979 to Crutchfield, et al., both incorporated herein
by reference. These polyacetal carboxylates can be prepared by bringing together under
polymerization conditions an ester of glyoxylic acid and a polymerization initiator.
The resulting polyacetal carboxylate ester is then attached to chemically stable end
groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline
solution, converted to the corresponding salt, and added to a surfactant.
[0040] Other detergency builder materials useful herein are the "seeded builder" compositions
disclosed in Belgian Patent No. 798,856, issued October 29, 1973, incorporated herein
by reference. Specific examples of such seeded builder mixtures are: 3:1 wt. mixtures
of sodium carbonate and calcium carbonate having 5 micron particle diameter; 2.7:1
wt. mixtures of sodium sesquicarbonate and calcium carbonate having a particle diameter
of 0.5 microns; 20:1 wt. mixtures of sodium sesquicarbonate and calcium hydroxide
having a particle diameter of 0.01 micron; and a 3:3:1 wt. mixture of sodium carbonate,
sodium aluminate and calcium oxide having a particle diameter of 5 microns.
Film-Forming Polymer
[0041] The compositions of the present invention also contain from about 0.1% to about 10%,
preferably from about 0.5% to about 7%, and more preferably from about 1% to about
4%, by weight of a film-forming polymer soluble in an aqueous slurry comprising the
organic surfactants, aluminosilicate materials, and neutral or alkaline salts herein.
It will be appreciated that the polymer must be at least partially soluble in the
slurry for it to dry to a film capable of cementing the granule walls together as
the slurry is dried. For optimum granule physical properties, the polymer should be
substantially soluble in the slurry, and is preferably completely soluble in the slurry.
The slurry will typically comprise a surfactant phase and the insoluble aluminosilicate
material suspended in a solution (often saturated) of the neutral or alkaline salt,
which preferably comprises sodium sulfate. The slurry will usually be alkaline in
nature due to the presence of the aluminosilicate material and either anionic surfactants
or alkaline salts. Since the slurry will generally be a strong electrolyte solution,
optimum solubility of the polymer is obtained when it is in the form of an at least
partially neutralized or substituted alkali metal, ammonium or substituted ammonium
(e.g., mono-, di- or triethanol ammonium) salt. The alkali metal, especially sodium,
salts are most preferred. While the molecular weight of the polymer can vary over
a wide range, it preferably is from about 1000 to about 500,000, more preferably is
from about 2000 to about 250,000, and most preferably is from about 3000 to about
100,000.
[0042] Suitable film-forming polymers herein include homopolymers and copolymers of unsaturated
aliphatic mono- or polycarboxylic acids. Preferred carboxylic acids are acrylic acid,
hydroxyacrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, aconitic
acid, crotonic acid, and citraconic acid. The polycarboxylic acids (e.g. maleic acid)
can be polymerised in the form of their anhydrides and subsequently hydrolyzed. The
copolymers can be formed of mixtures of the unsaturated carboxylic acids with or without
other copolymerisable monomers, or they can be formed from single unsaturated carboxylic
acids with other copolymerisable monomers. In either case, the percentage by weight
of the polymer units derived from non-carboxylic acids is preferably less than about
50%. Suitable copolymerisable monomers include, for example, vinyl chloride, vinyl
alcohol, furan, acrylonitrile, vinyl acetate, methyl acrylate, methyl methacrylate,
styrene, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, acrylamide, ethylene,
propylene and 3-butenoic acid.
[0043] Preferred polymers of the above group are the homopolymers and copolymers of acrylic
acid, hydroxyacrylic acid, or methacrylic acid, which in the case of the copolymers
contain at least about 50%, and preferably at least about 80%, by weight of units
derived from the acid. Particularly preferred polymers are sodium polyacrylate and
sodium polyhydroxyacrylate. Other specific preferred polymers are the homopolymers
and copolymers of maleic anhydride, especially the copolymers with ethylene, styrene
and vinyl methyl ether. These polymers are commercially available under the trade
names Versicol and Gantrez.
[0044] The polymerisation of acrylic acid homo- and copolymers can be accomplished using
free-radical initiators, such as alkali metal persulphates, acyl and aryl peroxides,
acyl and aryl peresters and aliphatic azocomcounds. The reaction can be carried out
in situ or in aqueous or non-aqueous solutions or suspensions. Chain- terminating
agents can be added to control the molecular weight. The copolymers of maleic anhydride
can be synthesised using any of the types of free-radical initiators mentioned above
in suitable solvents such as benzene or acetone, or in the absence of a solvent, under
an inert atmosphere. These polymerisation techniques are well known in the art. It
will be appreciated that instead of using a single polymeric aliphatic carboxylic
acid, mixtures of two or more polymeric aliphatic carboxylic acids can be used to
prepare the above polymers.
[0045] Other film-forming polymers useful herein include the cellulose sulfate esters such
as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methylcellulose
sulfate, and hydroxypropylcellulose sulfate. Sodium cellulose sulfate is the most
preferred polymer of this group.
[0046] Other suitable film-forming polymers are the carboxylated polysaccharides, particularly
starches, celluloses and alginates, described in U.S. Patent 3,723,322, Diehl, issued
March 27, 1973; the dextrin esters of polycarboxylic acids disclosed in U.S. Patent
3,919,107, Thompson, issued November 11, 1975; the hydroxyalkyi starch ethers, starch
esters, oxidized starches, dextrins and starch hydrolysates described in U.S. Patent
3,803,285, Jensen, issued April 9, 1974; and the carboxylated starches described in
U.S. Patent 3,629,121, Eldib, issued December 21, 1971; all incorporated herein by
reference. Preferred polymers of the above group are the carboxymethyl celluloses.
[0047] Particularly preferred polymers for use herein are copolymers of acrylamide and acrylate
having a molecular weight of from about 3,000 to about 100,000, preferably from about
4,000 to about 20,000, and an acrylamide content of less than about 50%, preferably
less than about 20%, of the polymer. Most preferably, the polymer has a molecular
weight of from about 4,000 to about 10,000 and an acrylamide content of from about
5% to about 15%. Such a polymer acts to increase the percentage of a crutcher mix
that is in the aqueous (lye) phase. This improves the rate at which droplets of the
crutcher mix will dry in a spray tower and can desirably increase the density of the
resulting detergent granules when, for example, large amounts of sodium sulfate or
other high-density inorganic salt is in the lye phase.
[0048] It has also been found, surprisingly, that a mixture of the preferred polyacrylamide
copolymer and from about 0.5% to about 2%, preferably from about 0.5% to about 1%,
by weight of a low-ratio silicate, i.e., one having a ratio of from about 1.0 to about
1.4, provides optimum granule structure and solubility. In an especially preferred
aspect, the crutcher mix contains additional alkalinity, e.g., by way of added sodium
carbonate at a level of from about 1% to about 30% or its alkalinity equivalent, as
a water-soluble inorganic material and contains less than about 50% sodium sulfate,
by weight of the finished product, preferably less than about 30%, to achieve normal
densities without additional additives.
[0049] Other ingredients commonly used in detergent compositions can be included in the
compositions of the present invention. These include color speckles, bleaching agents
and bleach activators, suds boosters or suds suppressors, anti-tarnish and anti-corrosion
agents, soil suspending agents, soil release agents, dyes, fillers, optical brighteners,
germicides, pH adjusting agents, non-builder alkalinity sources, hydrotropes, enzymes,
enzyme-stabilizing agents, and perfumes.
[0050] The following non-limiting examples illustrate the detergent compositions of the
present invention.
[0051] All percentages, parts, and ratios used herein are by weight unless otherwise specified.
[0052] The following granular detergent compositions were evaluated using the indicated
tests.
Compression Test
[0053] The granules are poured into a standard cylinder and compressed by applying a 20
pound weight for about 60 seconds. The difference in height in inches is the compression
grade. Lower numbers are therefore better. Grades of less than about 30 are acceptable.
Cake Test
[0054] The compressed, unsupported cylinder of granules created by the compression test
is fractured by applying a weight to the top until the cylinder fractures. The weight
in pounds required to fracture the cylinder is the cake grade. For products prepared
in a small 10' diameter tower, grades of less than about 20 are acceptable.
Black Fabric Test
[0055] The detergent composition is dissolved in water under standard conditions and filtered
with suction through a black knit fabric and graded against photographic standards.
Grades of 8 to 10 are acceptable.
EXAMPLE I
[0056]

[0057] The above composition had a black fabric grade of 4. Grades of 10 were obtained when
the 8.5 parts of sodium silicate was replaced with: 8.5 parts of sodium sulfate; 1.5
parts of sodium carboxymethyl cellulose and 7 parts of sodium sulfate; 3 parts of
sodium carboxymethyl cellulose and 5.5 parts of sodium sulfate; 0.8 parts of sodium
cellulose sulfate and 7.7 parts of sodium sulfate; and 3 parts of sodium cellulose
sulfate and 5.5 parts of sodium sulfate.
EXAMPLES
[0058]

[0059] Under stress storage conditions, e.g., high humidity and temperature, the composition
of Example II exhibits marginal cake and compression grades.
1. A granular detergent composition comprising:
(a) from about 5% to about 40% by weight of an organic surfactant selected from the
group consisting of anionic, nonionic, zwitterionic, ampholytic and cationic surfactants,
and mixtures thereof;
(b) from about 10% to about 60% by weight of a finely divided aluminosilicate ion
exchange material selected from the group consisting of:
(1) crystalline aluminosilicate material of the formula:

wherein z and y are at least 6, the molar ratio of z to y is from 1.0 to 0.5 and x
is from 10 to 264, said material having a particle size diameter of from about 0.1
micron to about 10 microns, a calcium ion exchange capacity of at least about 200
mg. CaCO3 eq./g. and a calcium ion exchange rate of at least about 2 grains Ca++/gallon/minute/gram/gallon;
(2) amorphous hydrated aluminosilicate material of the empirical formula:

wherein M is sodium, potassium, ammonium, or substituted ammonium, z is from about
0.5 to about 2 and y is 1, said material having a magnesium ion exchange capacity
of at least about 50 milligram equivalents of CaCO3 hardness per gram of anhydrous aluminosilicate and a Mg exchange rate of at least
about 1 grain/gallon/minute/gram/gallon; and
(3) mixtures thereof; and
(c) from about 5% to about 75% by weight of a water-soluble neutral or alkaline salt;
and
(d) from about 0.1% to about 10% by weight of a film-forming polymer soluble in an
aqueous slurry comprising the above components; said composition containing less than
about 10% by weight of phosphate materials and less than about 3% by weight of alkali
metal silicate materials.
2. A composition according to Claim 1 wherein the organic surfactant represents from
10% to 30% by weight and is selected from the group consisting of linear alkylbenzene
sulfonates containing from about 11 to 14 carbon atoms in the alkyl group, tallowalkyl
sulfates; coconutalkyl glyceryl ether sulfonates; alkyl ether sulfates wherein the
alkyl moiety contains from about 14 to 18 carbon atoms and wherein the average degree
of ethoxylation is from about 1 to 4; olefin or paraffin sulfonates containing from
about 14 to 16 carbon atoms; alkyldimethyl amine oxides wherein the alkyl group contains
from about 11 to 16 carbon atoms; alkyldimethylammonio propane sulfonates and alkyldimethylammonio
hydroxy propane sulfonates wherein the alkyl group contains from about 14 to 18 carbon
atoms; soaps of higher fatty acids containing from about 12 to 18 carbon atoms; condensation
products of C9-C15 alcohols with from about 4 to 8 moles of ethylene oxide, and mixtures thereof.
3.. A composition according to Claim 1 comprising from about 15% to about 30% by weight
of the aluminosilicate ion exchange material of the formula

wherein x is from about 20 to about 30.
4. A composition according to Claim 1 comprising from about 10% to about 60% by weight
of the water-soluble neutral or alkaline salt.
5. A composition according to Claim 1 comprising from about 0.5% to about 7% by weight
of the film-forming polymer having a molecular weight of from about 1000 to about
500,000.
6. A composition according to Claim 1 wherein the . film-forming polymer is an at
least partially neutralized salt of a homopolymer or copolymer of an unsaturated carboxylic
acid selected from the group consisting of acrylic acid, hydroxyacrylic acid, methacrylic-acid,
maleic acid, fumaric acid, itaconic acid, aconitic acid, crotonic acid, and citraconic
acid.
7. A composition according to Claim 6 wherein the film-forming polymer is selected
from: a copolymer of acrylamide and sodium acrylate having a molecular weight of from
about 3000 to about 100,000 and an acrylamide content of less than about 50%, preferably
from about 5% to about 15%; and sodium polyacrylate or sodium polyhydroxyacrylate.
8. A composition according to Claim 1 wherein the film-forming polymer is a copolymer
of vinyl methyl ether and maleic anhydride.
9. A composition according to Claim 1 wherein the film-forming polymer is selected
from the group consisting of salts of cellulose acetate sulfate, cellulose sulfate,
hydroxyethyl cellulose sulfate, methylcellulose sulfate, and hydroxypropylcellulose
sulfate.
10. A composition according to Claim 1 containing from about 0.5% to about 2% by weight
of sodium or potassium silicate having a molar ratio of SiO2 to alkali metal oxide of from about 1 to about 1.4.